CN114515567A - Biological magnetic nano composite material, preparation method and application thereof - Google Patents
Biological magnetic nano composite material, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a biomagnetic nano composite material, a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, dispersing ferroferric oxide particles in an aqueous solution to obtain an aqueous solution of ferroferric oxide, and then adding a ferrite solution into the aqueous solution of ferroferric oxide to obtain a reduction mixed solution; dropwise adding a borohydride solution into the reduction mixed solution to perform reduction reaction to obtain the nano zero-valent iron-ferroferric oxide nano material, wherein the whole process is completed under the protection of nitrogen; s2, embedding the nano zero-valent iron-ferroferric oxide nano material obtained in the step S1 with polyethyleneimine to obtain the biomagnetic nano composite material. The biomagnetic nanocomposite material obtained by the invention can be used for repairing acidic arsenic-containing wastewater, and can rapidly and efficiently repair the acidic arsenic-containing wastewater.
Description
Technical Field
The invention relates to purification of arsenic-containing wastewater, in particular to a biomagnetic nano composite material, and a preparation method and application thereof.
Background
Arsenic (As) pollution is a worldwide environmental problem that has attracted widespread attention due to its adverse effects on human health worldwide. It is reported that arsenic-containing high-concentration wastewater is discharged from industrial sources more than 4 ten thousand tons every year due to rapid development of industry. The main industrial processes responsible for arsenic contamination are non-ferrous metal smelting processes, particularly smelting operations and flue gas pickling recovery, which produce highly acidic wastewater with large amounts of high concentrations of arsenic. Arsenic is found in aqueous environments primarily as two inorganic compounds, arsenite (as (iii)) and arsenate (as (v)). Importantly, as (iii) is approximately 60 times more toxic than as (v) as compared to as (v). Studies have shown that prolonged exposure to arsenic-contaminated water can have deleterious effects on the body and mind, such as skin damage, bladder cancer, liver cancer, kidney cancer, nasal cavity cancer, and even death in extreme cases.
Various conventional techniques, such as coagulation, membrane separation, advanced oxidation, adsorption and ion exchange, have been used to remove arsenic from aqueous environments. Coagulation easily causes secondary pollution, and water pollutants are changed into solid pollutants, so that the solid pollutants are more difficult to remove; advanced oxidation and membrane dissociation can remove arsenic from aqueous environments quickly and efficiently, but the additional energy and expensive membranes add to the cost of the process. Also, under strongly acidic conditions, the membrane is more susceptible to damage and reduced lifetime. The adsorption method is considered to be a promising method due to its simple operation, low cost, and rapid and effective removal of arsenic. Therefore, it is necessary to develop an adsorbent which is environmentally friendly and can have a good adsorption effect under strongly acidic conditions.
The nanometer zero-valent iron (nZVI) is widely applied to the remediation of heavy metals in polluted water bodies due to the characteristics of low cost, high reaction activity, easy obtainment, strong reducibility and the like, and is a high-efficiency reaction medium material for the remediation of underground water and industrial water. Unfortunately, nZVI has some limitations such as its particles are prone to agglomeration and precipitation, rapid deactivation and low electron utilization due to the formation of a surface passivation layer and unnecessary hydrogen evolution reaction, which shortens its reaction life and significantly inhibits its application in water remediation. Furthermore, the direct use of nZVI in water creates secondary pollution, as nanoparticles themselves are considered an emerging class of pollutants.
In the existing research, the chinese patent publication No. CN103862037B discloses a preparation and pretreatment method of a biomaterial embedded zero-valent iron-ferroferric oxide double nano system, and the prepared iron-containing pellets can be applied to the field of conventional zero-valent iron pollution remediation, and meanwhile, the potential risk in the application of nano materials is reduced, and the purpose of safe and efficient treatment is achieved. However, the preparation time is relatively long, and firstly ferroferric oxide needs to be prepared, and then the zero-valent iron-ferroferric oxide nano material is synthesized on the basis; a cross-linking agent, a solid and liquid are added, and acidification and reduction treatment are required, so that secondary pollution is caused to the water environment; the embedding material only has an embedding effect and does not have a removing effect on target pollutants; the target pollutant of the patent is Cr (VI) removal of an aqueous solution, and the target pollutant is not related to acid arsenic-containing wastewater.
In view of the above, to solve or at least alleviate the above drawbacks, the present invention provides a biomagnetic nanocomposite material, and a preparation method and application thereof.
Disclosure of Invention
The invention mainly aims to provide a biomagnetic nano composite material, a preparation method and application thereof, and aims to solve the technical problems.
In order to achieve the above object, the present invention provides a method for preparing a biomagnetic nanocomposite, comprising the steps of:
s1, preparing a nano zero-valent iron-ferroferric oxide nano material;
further, the preparation of the nano zero-valent iron-ferroferric oxide nano material comprises the following steps:
s11, dispersing the ferroferric oxide particles in an aqueous solution to obtain a ferroferric oxide aqueous solution, and then adding a ferrite solution into the ferroferric oxide aqueous solution to obtain a reduction mixed solution;
s12, dropwise adding a borohydride solution into the reduction mixed solution to perform reduction reaction to obtain the nano zero-valent iron-ferroferric oxide nano material;
wherein, the whole process of the step S11 and the step S12 is carried out under the protection of nitrogen.
Further, the step S12 further includes: and after the reduction reaction is carried out, sequentially separating, washing and drying the product of the reduction reaction to obtain the nano zero-valent iron-ferroferric oxide nano material.
Further, the ferrous salt solution comprises one of a ferrous sulfate solution, a ferrous chloride solution and a ferrous nitrate solution; the borohydride solution comprises sodium borohydride or potassium borohydride solution.
Further, BH in said borohydride solution4 -Solubility of (2) and Fe in ferrous salt solution2+Is greater than 2.
Further, in the nano zero-valent iron-ferroferric oxide nano-material, Fe0And Fe3O4The mass ratio of (A) to (B) is 1: 0.3-1: 5.
S2, embedding the nano zero-valent iron-ferroferric oxide nano material by using polyethyleneimine to obtain the biological magnetic nano composite material.
Further, the step S2 includes:
s21, dissolving polyethyleneimine in absolute ethyl alcohol to obtain a polyethyleneimine solution; dissolving a nano-grade zero-valent iron-ferroferric oxide nano-grade material in a buffer solution to obtain a zero-valent iron-ferroferric oxide nano-grade solution;
s22, mixing the polyethyleneimine solution and the zero-valent iron-ferroferric oxide nano-solution to perform embedding reaction; and then sequentially separating, washing and drying the embedding reaction product to obtain the biomagnetic nano composite material.
Further, in the step S21, the volume ratio of the absolute ethyl alcohol to the buffer solution is 1: 0.5-1: 1;
In the step S22, the concentration of the polyethyleneimine after being dissolved in the absolute ethanol and the buffer solution is 5mg/L to 15mg/L, that is, the initial concentration of the polyethyleneimine during the embedding process is 5mg/L to 15 mg/L.
The invention also provides a biomagnetic nanocomposite material which is characterized by being prepared by the preparation method.
The invention also provides an application of the biomagnetic nanocomposite material in acidic arsenic-containing wastewater.
The technical principle of the invention comprises:
in the invention, Fe3O4Synthesis of Fe for substrate Material3O4the-nZVI double nano particles are embedded by utilizing biopolymer Polyethyleneimine (PEI) to synthesize the biomagnetic nano composite material, so that the acidic arsenic-containing wastewater can be quickly and efficiently repaired.
1. Polyethyleneimine (PEI) is an environment-friendly polymer, can be dissolved in ethanol and water, and contains abundant primary amine, secondary amine and tertiary amine groups on a polymer chain, so that the PEI can exist as a polymer cation in ethanol or water, can neutralize and adsorb all anions, and can also chelate heavy metal ions. On the other hand, Fe3O4the-nZVI double nanoparticles exhibit a negative surface charge under alkaline conditions, and therefore, in Tris-buffer solution (pH 8.5), Fe 3O4the-nZVI double nanoparticles and the PEI can interact with each other through electrostatic attraction, so that the use of a cross-linking agent and a reinforcing liquid is avoided, and the embedding effect is achieved. Furthermore, as mentioned above, PEI contains abundant amine functional groups, and under acidic conditions, the amine functional groups in PEI are protonated, so that the surface of the biomagnetic nanocomposite material of the invention has a large amount of surfaceAnd arsenic ions belong to anionic contaminants in aqueous solution, in particular as (v), the ionic morphology of which varies with pH as follows: h3AsO4(pH<2)，H2AsO4 -(2≤pH≤6.1)，HAsO4 2-(pH is not less than 6.1 and not more than 11.5), and AsO4 3-(pH>11.5) therefore Fe embedding with PEI3O4the-nZVI double nanoparticles can quickly and efficiently repair the acidic arsenic-containing wastewater.
2. Aiming at the removal of As (III) in aqueous solution, the invention utilizes Fe3O4Strengthening nZVI, Fe3O4Is a multivalent iron oxide, has stable physicochemical properties and wide sources, and related researches propose Fe3O4Can be used as a conductor to accelerate the electron transfer between the nZVI and a pollution target object, and the ferroferric oxide has weak magnetism, and the research shows that the weak magnetic field can influence the charged ion distribution on the surface of the nano zero-valent iron and can continuously generate Fe3+Thereby a part of Fe3+Capable of oxidizing As (III) to As (V), a portion of which is coordinated to As (III); oxidizing As (III) to As (V) fraction, and removing by electrostatic attraction between PEI and As (V).
3. PEI not only plays a role in embedding to avoid the oxidation of the iron nanoparticles, but also effectively enables Fe3O4Compared with the dispersion of the-nZVI double nanoparticles, the iron nanoparticles are prevented from agglomerating, and more active sites are provided for removing arsenic in the acidic wastewater.
Compared with the prior art, the invention has the following advantages:
1. the price is low; commercially available Fe3O4Namely, Fe can be synthesized for the substrate material3O4-nZVI double nanoparticles, embedded material PEI is also readily available and cheap. The synthetic method is green and simple, and the energy consumption is low; the preparation process does not need treatment methods such as cross-linking agent, acidification and the like, so that the use of a large amount of medicament and secondary pollution to the environment are avoided;
2. under the acidic condition, the better removal effect can still be kept; most of the materials are structurally damaged under acidic conditions, thereby causingAiming at the defect that the method is difficult to be applied to the remediation of acidic arsenic-containing wastewater due to the low pollutant removal performance and other results, the invention utilizes PEI to embed Fe3O4The biomagnetic nano composite material synthesized by the-nZVI double nano particles has a complete structure under an acidic condition, has a large amount of positive charges on the surface, can keep fast and efficiently removing arsenic pollution in acidic wastewater, and can be better applied to the repair of the acidic arsenic-containing wastewater.
3. Under the condition of high concentration, the better removal effect can still be kept; in the existing research, the Chinese patent with publication number CN103862037B discloses a preparation and pretreatment method of a biomaterial embedded zero-valent iron-ferroferric oxide double nano system, and the removal rate of the prepared iron-containing pellets is obviously reduced along with the increase of the concentration of pollutants, and when the concentration of the pollutants is 40mg/L, the removal rate in 12 hours is 79.5%, and the complete removal time is unknown. The removal performance of the material is not obviously changed along with the improvement of the concentration of pollutants, when the concentration of arsenic ions is 300mg/L, the removal efficiency of the material to As (III) can still reach 96.64%, and the removal efficiency of As (V) reaches 86.07%. Even when the arsenic ion concentration is increased to 1000mg/L, the good removal performance can be maintained.
4. The iron precipitation concentration is low; considering that the iron nano particles can cause secondary pollution to the environment, the invention also tests the iron precipitation concentration in the aqueous solution, and finds that the PEI is utilized to embed Fe3O4After the-nZVI double nanoparticles are adopted, the concentration of iron ions separated out can be almost ignored, the arsenic removal effect is increased, the high-efficiency treatment capacity of the nano composite material can be kept, the nano-sized biotoxicity is reduced, the loss of the particles is greatly reduced, and therefore the environmental risk caused by the migration and conversion processes of the nano composite material in use is reduced.
5. The use of PEI for embedding prevents Fe3O4Rapid oxidation of nZVI double nanoparticles, increased service life.
6. The separation operation is simple, and in practical application, the effect of complete separation can be achieved only by using simple membrane separation, thereby being beneficial to the reutilization of a system. In addition, the embedding system can be applied to an aerobic environment, and compared with pure nano zero-valent iron particles which are rapidly passivated in the aerobic environment, the application range is expanded.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) image of the nano-sized zero-valent iron-ferroferric oxide nano-material obtained in example 2;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the biomagnetic nanocomposite obtained in example 2;
FIG. 3 is a sample diagram of the biomagnetic nanocomposite obtained in example 2;
FIG. 4 is a graph showing the effect of the data on the removal of As (III) and As (V) under different pH conditions in the biomagnetic nanocomposite material of example 5;
FIG. 5 is a graph showing the effect of the data on the removal of As (III) and As (V) in example 6 under different contact time conditions;
FIG. 6 is a graph showing the effect of the removal of As (III) and As (V) from the biomagnetic nanocomposite material of example 7 under different initial arsenic concentrations.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any number between the two endpoints are optional unless otherwise specified in the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and are intended to be open ended, i.e., to include any methods, devices, and materials similar or equivalent to those described in the examples.
The invention provides a preparation method of a biomagnetic nano composite material, which comprises the following steps:
s1, preparing a nano zero-valent iron-ferroferric oxide nano material;
the step S1 specifically includes:
s11, dispersing the ferroferric oxide particles in an aqueous solution to obtain a ferroferric oxide aqueous solution, and then adding a ferrite solution into the ferroferric oxide aqueous solution to obtain a reduction mixed solution;
s12, dropwise adding a borohydride solution into the reduction mixed solution to perform reduction reaction to obtain the nano zero-valent iron-ferroferric oxide nano material;
wherein, the whole process of the step S11 and the step S12 is carried out under the protection of nitrogen.
S2, embedding Fe by using Polyethyleneimine (PEI)3O4-nZVI double nanoparticles, resulting in the biomagnetic nanocomposite.
In the above embodiment, a liquid phase reduction method is used to uniformly load nano zero-valent iron on ferroferric oxide, wherein the ferroferric oxide can be used as a stabilizer for nano zero-valent iron particles to prepare a nano zero-valent iron-ferroferric oxide nano-material, and on the other hand, the ferroferric oxide can strengthen the nano zero-valent iron and improve the capacity of removing arsenic pollution in acidic wastewater; then, appropriate biological materials are selected to carry out embedding treatment on the double-nano materials to obtain a biological magnetic nano composite material; the biological magnetic nano composite material is used for repairing acidic high-concentration arsenic-containing wastewater, and the biological material and the double nano materials can perform synergistic adsorption on arsenic ions in a water environment, so that a good removal effect is achieved.
As a specific example of the above embodiment, the preparation method of the biomagnetic nanocomposite material may specifically be:
s1, preparing the nano zero-valent iron-ferroferric oxide nano material.
Further, in step S1, the preparation of the nano zero-valent iron-ferroferric oxide nano-material includes the steps of:
S11, mixing 0.12g of Fe3O4Dissolving the nanoparticles in 200mL deoxygenated water, stirring for 1h, transferring the solution to a 500mL Erlenmeyer flask, and introducing nitrogen to avoid Fe3O4Oxidation of the nanoparticles;
s12, adding 2g FeSO into the solution4·7H2O, stirring for 0.5h to ensure FeSO4·7H2Completely dissolving O;
s13, slowly adding 200mL of 0.25mol/L NaBH into the mixed solution4And stirring the solution for 1 hour after the dropwise addition is finished so as to ensure the complete reduction reaction.
S14, stopping introducing nitrogen after the reaction is completed, filtering the obtained product, washing the product with deoxygenated water for 3-5 times, and finally freeze-drying the product for 24 hours to obtain Fe3O4-nZVI double nanoparticles.
S2, embedding Fe by using Polyethyleneimine (PEI)3O4-nZVI double nanoparticles, obtaining said biomagnetic nanocomposite.
Further, the step S2 includes the steps of:
s21, dissolving 1g of PEI in 60mL of absolute ethyl alcohol, and stirring for 0.5h to ensure that polyethyleneimine is completely dissolved;
s22, adding 0.1g of Fe3O4Dissolving the-nZVI double nanoparticles in 40mL of Tris-buffer solution, stirring for 0.5h, mixing the two solutions, performing ultrasonic treatment for 0.5h, and placing the mixed solution in a constant temperature oscillation box to oscillate for 24h at 25 ℃;
and S23, after the reaction is completed, filtering the obtained product, washing the product with deoxygenated water for 3-5 times, and finally freeze-drying the product for 24 hours to obtain the biomagnetic nanocomposite.
Based on the preparation method, the invention also provides a biomagnetic nanocomposite material which is prepared by adopting the preparation method.
Based on the characteristics of the biomagnetic nanocomposite material, the invention also provides an application of the biomagnetic nanocomposite material in the remediation of acidic arsenic-containing wastewater, particularly an application in the remediation of acidic high-concentration arsenic-containing wastewater, such as application in arsenic-containing wastewater with pH of 3 and arsenic concentration of 1000 mg/L.
Example 1
This example explores Fe0And Fe3O4The specific implementation steps of the optimal mass ratio are as follows:
(1) preparing nanometer zero-valent iron-ferroferric oxide nanometer materials with different proportions: 0.04g, 0.06g, 0.2g and 0.6g of Fe were weighed out respectively3O4Dissolving in 100mL deionized water, stirring for 1h, transferring the solution to a 500mL three-neck flask respectively, introducing nitrogen, and adding 1g FeSO into the three-neck flask respectively4·7H2O, stirring for 0.5h to ensure FeSO4·7H2Complete dissolution of O, Fe0:Fe3O4The mass ratio of (A) to (B) is 1: 0.3, 1: 1. 1: 3 and 1: 5, stirring to fully dissolve the mixture; dropwise adding 100mL of 0.25mol/LNaBH into the obtained mixed solution4A solution to perform a reduction reaction; after reacting for 1h, stopping introducing nitrogen, filtering the obtained product, washing the product with deoxygenated water for 3-5 times, and finally freeze-drying for 24h to obtain the product Fe of the same mass ratio3O4-nZVI double nanoparticles (Fe)3O4-nZVI)。
(2) Respectively weighing 0.01g of nano zero-valent iron-ferroferric oxide nano materials prepared by the steps in different mass ratios, and then respectively adding the nano zero-valent iron-ferroferric oxide nano materials into 10mL of 300mg/L As (III) and As (V) aqueous solution. Adjusting the initial pH of the solution to 3.0, and oscillating in a gas bath constant-temperature oscillation box with the temperature controlled at 25 ℃ and the rotation speed of 180 r/min. After oscillation for 24h, sampling, measuring the solubility of As (III) and As (V) in the detection solution by using an inductively coupled plasma atomic emission spectrometer (ICP-OES), and calculating the adsorption quantity of each material to As (III) and As (V).
The removal conditions of As (III) and As (V) by nano zero-valent iron-ferroferric oxide nano materials with different mass ratios are shown in the table 1:
| 1：0.3 | 1：1 | 1：3 | 1：5 | |
| As(III) | 292.2mg/g | 159.72mg/g | 50.65mg/g | 95.6mg/g |
| As(V) | 213.54mg/g | 189.3mg/g | 116.45mg/g | 165.66mg/g |
as can be seen from Table 1, the optimum Fe0：Fe3O4The mass ratio of (1): 0.3 Fe is the least effective for removing As (III) and As (V)0：Fe3O4The mass ratio of (1): 3.
example 2
This example uses the best Fe in example 10：Fe3O4Preparing a Polyethyleneimine (PEI) embedded nano zero-valent iron-ferroferric oxide nano material according to the mass ratio to obtain the biological magnetic nano composite material, wherein the specific preparation steps are as follows:
(1) preparing a nano zero-valent iron-ferroferric oxide double nano material: first 0.12g Fe was weighed 3O4Dissolved in 200mL of deionized water, stirred for 1 hour, transferred to a 500mL three-neck flask and purged with nitrogen, and then 2g of FeSO was added to the three-neck flask4·7H2O, stirring for 0.5h to ensure FeSO4·7H2Complete dissolution of O, Fe0:Fe3O4The mass ratio of the components is 1:0.3, and the components are stirred to be fully dissolved; dropwise adding 200mL of 0.25mol/L NaBH into the obtained mixed solution4A solution to perform a reduction reaction; after reacting for 1h, stopping introducing nitrogen, filtering the obtained product, washing the product with deoxygenated water for 3-5 times, and finally freeze-drying for 24h to obtain Fe3O4-nZVI double nanoparticles (Fe)3O4-nZVI)。
(2) Embedding the biological material: firstly, 1g of PEI (10mg/L) is dissolved in 60mL of absolute ethyl alcohol, and after stirring for 0.5h, the polyethyleneimine is ensured to be completely dissolved; 0.1g of Fe3O4Dissolving the-nZVI double nanoparticles in 40mL of Tris-buffer solution (pH 8.5), stirring for 0.5h, mixing the two solutions, performing ultrasonic treatment for 0.5h, and placing the mixed solutions in a constant-temperature oscillation box to oscillate for 24h at 25 ℃, wherein the volume ratio of the Ethanol (absolute ethyl alcohol) to the Tris-buffer solution is 3: 2. Inverse directionAnd after the reaction is completed, filtering the obtained product, washing the product with deoxygenated water for 3-5 times, and finally freeze-drying the product for 24 hours to obtain the biomagnetic nano composite material.
FIG. 1 is a Scanning Electron Microscope (SEM) image of the nano-sized zero-valent iron-ferroferric oxide nano-material obtained in example 2; FIG. 2 is a Transmission Electron Microscope (TEM) image of the biomagnetic nanocomposite obtained in example 2; FIG. 3 is a sample diagram of the biomagnetic nanocomposite obtained in example 2.
Referring to fig. 1, the biomagnetic nanocomposite material of the present invention is black powder; referring to FIG. 1, Fe3O4the-nZVI double nanoparticles are agglomerated and precipitated, so that the electron utilization rate is low, the reaction life is shortened, and the application of the-nZVI double nanoparticles in water remediation is obviously inhibited; referring to fig. 2, after being embedded by PEI, the biomagnetic nanocomposite is significantly dispersed, and a layer of film can be seen on the outer layer, which can be judged as a polyethyleneimine film, thus proving successful modification of the material.
Example 3
The method for researching the removal of As (III) and As (V) from the biomagnetic nano composite material obtained by embedding pure nano zero-valent iron, pure ferroferric oxide, nano zero-valent iron-ferroferric oxide nano material and polyethyleneimine comprises the following specific steps:
(1) the synthesis of the nano zero-valent iron comprises the following steps: weighing 2g of FeSO4·7H2Dissolving O in 200mL of deionized water, pouring into a 500mL three-neck flask, introducing nitrogen, stirring to fully dissolve the O, and dropwise adding 0.25M 200mL of NaBH into the mixed solution4And (3) carrying out reduction reaction on the solution, stopping introducing nitrogen after 1h of reaction, filtering the obtained product, washing the product with deoxygenated water for 3-5 times, and finally carrying out freeze drying for 24h to obtain the nano zero-valent iron particles.
(2) The steps for synthesizing the nano zero-valent iron-ferroferric oxide nano material and the embedded biomagnetic nanocomposite material obtained by the polyethylene imine are as described in example 2.
(3) Respectively weighing 0.01g of the pure nano zero-valent iron, the pure ferroferric oxide, the nano zero-valent iron-ferroferric oxide double nano material prepared by the steps and the biological magnetic nano composite material obtained after the embedding of the polyethyleneimine, and then respectively adding the nano magnetic nano composite material into 10mL of 300mg/L As (III) and As (V) aqueous solution. Adjusting the initial pH of the solution to 3.0, and oscillating in a gas bath constant-temperature oscillation box with the temperature controlled at 25 ℃ and the rotation speed of 180 r/min. After oscillation for 24h, sampling, measuring the solubility of As (III) and As (V) in the detection solution by using an inductively coupled plasma atomic emission spectrometer (ICP-OES), and calculating the adsorption quantity of each material to As (III) and As (V).
The removal conditions of As (III) and As (V) of the pure nano zero-valent iron, ferroferric oxide, nano zero-valent iron-ferroferric oxide nano material and the biomagnetic nano composite material obtained after the embedding of polyethyleneimine are shown in Table 2:
| Fe3O4 | nZVI | Fe3O4-nZVI | Fe3O4-nZVI-PEI | |
| As(III) | 24.15mg/g | 267.96mg/g | 292.2mg/g | 282.24mg/g |
| As(V) | 31.8mg/g | 195.42mg/g | 213.54mg/g | 258.86mg/g |
as can be seen from Table 2, the pure ferroferric oxide has the worst removal effect on As (III) and As (V), and the pure nano zero-valent iron has the better removal effect on As (III) and As (V); the removal effect of the nano zero-valent iron-ferroferric oxide nano material on As (III) and As (V) is further improved, and the fact that the ferroferric oxide can strengthen the removal capability of the nano zero-valent iron is proved; after PEI is embedded, although the removal effect of As (III) is slightly reduced, probably because part of the active sites are covered by the polyethyleneimine molecular film, the adsorption capacity is slightly reduced. However, the adsorption capacity of As (V) is further improved, and the fact that PEI can perform synergistic action with the nano zero-valent iron-ferroferric oxide nano material is proved, so that As (V) achieves a high removal effect, and the PEI can still be applied to the remediation of acidic arsenic-containing wastewater.
Example 4
The method for researching the influence of different polyethyleneimine concentrations on the removal capacity of the prepared biomagnetic nano material when the polyethyleneimine-embedded nano zero-valent iron-ferroferric oxide nano material is prepared by the method comprises the following specific steps:
in this embodiment, different concentrations of polyethyleneimine (concentration of polyethyleneimine dissolved in anhydrous ethanol and buffer solution) are used to prepare embedded nano zero-valent iron-ferroferric oxide nano-material, and used to treat as (iii) and as (v). The other preparation steps are the same as example 2, and the removal steps for As (III) and As (V) are the same as example 3.
Table 3 shows the removal effect of the biomagnetic nanocomposites prepared with different polyethyleneimine concentrations on as (iii) and as (v):
| 5mg/L | 10mg/L | 15mg/L | |
| As(III) | 223.56mg/g | 282.24mg/g | 280.86mg/g |
| As(V) | 238.74mg/g | 258.86mg/g | 237.72mg/g |
as can be seen from Table 3, as the concentration of polyethyleneimine is increased from 5mg/L to 10mg/L, the adsorption amounts of As (III) and As (V) of the prepared biomagnetic nanocomposite are increased; but the concentration of the polyethyleneimine is continuously increased, and the adsorption quantity of the prepared biomagnetic nano composite material to As (III) and As (V) is reduced; this is probably because a thick film is formed on the surface of the nano zero-valent iron-ferroferric oxide nano-material by continuously increasing the concentration of polyethyleneimine, so that the reaction between the nano zero-valent iron-ferroferric oxide nano-material and pollutants is prevented, adsorption sites are reduced, and the adsorption amount is reduced. Therefore, it is preferable that the concentration of polyethyleneimine is 10 mg/L.
Example 5
The method is used for researching the removal condition and iron precipitation condition of the biomagnetic nano composite material on As (III) and As (V) when the initial pH of the solution is different, and comprises the following specific steps:
in this example, the removal of as (iii) and as (v) and the iron precipitation of the biomagnetic nanocomposite were investigated when the initial pH of the arsenic solution was 1, 3, 5, 7, 9, and 11.
0.01g of each of the biomagnetic nanocomposites prepared by the above example 2 is weighed into 10mL of 300mg/L aqueous solution of As (III) and As (V), followed by adjusting the respective solutions of As (III) and As (V) to different pH values using 0.1M HCl or NaOH, for example, to pH values of 1, 3, 5, 7, 9, 11, and shaking in a gas bath incubator at a temperature of 25 ℃ and a rotation speed of 180 rpm. After oscillating for 24 hours, sampling, measuring the solubility of As (III), As (V) and Fe in the detection solution by using an inductively coupled plasma atomic emission spectrometer (ICP-OES), and calculating the adsorption amount of each material to As (III) and As (V).
Different initial pH values and corresponding adsorption amounts are shown in FIG. 4, and as can be seen from FIG. 4, with the increase of the pH value of the solution, the adsorption amounts of the biomagnetic nanocomposite to As (III) and As (V) are increased and then decreased, and it can be found that the adsorption amount is the best when the pH value is 3.0, which proves that the biomagnetic nanocomposite provided by the invention has better adsorption performance under acidic conditions and has good application prospects for removing industrial acidic high-concentration wastewater; and when the pH value is 3.0, the concentration of iron in the solution is almost 0, which proves the stability of the material under the acidic condition and avoids causing secondary pollution.
Example 6
The removal conditions of the biomagnetic nanocomposite material on As (III) and As (V) under different contact time conditions are studied, and the specific steps are as follows:
in this example, the removal of As (III) and As (V) by the biomagnetic nanocomposite material is studied when the contact time is 5min, 10min, 20min, 40min, 60min, 120min, 180min, 240min, 360min, 12h, and 24 h.
0.01g of the biomagnetic nanocomposite prepared by the above example 2 was weighed out and added to 10mL of 300mg/L aqueous solution of As (III) and As (V), followed by adjusting the pH of the solution of As (III) and As (V) to 3 with 0.1M HCl or NaOH, respectively, and shaking the solution in a gas bath constant temperature shaking chamber at a temperature of 25 ℃ and a rotation speed of 180 rpm. After stirring for a preset time, sampling, measuring As (III) and As (V) in the detection solution by using an inductively coupled plasma atomic emission spectrometer (ICP-OES), and calculating the adsorption amount of each material to As (III) and As (V).
The removal of As (III) and As (V) from the biomagnetic nanocomposite material with different contact times is shown in FIG. 5. Referring to fig. 5, as the contact time increases, the adsorption amounts of as (iii) and as (v) of the biomagnetic nanocomposite material rapidly increase and then gradually reach an equilibrium at about 2 h.
Example 7
The method for researching the removal conditions of As (III) and As (V) by the biomagnetic nanocomposite material in different initial concentrations of arsenic solutions comprises the following specific steps:
this example demonstrates the removal of As (III) and As (V) from a biomagnetic nanocomposite material at initial arsenic concentrations of 5mg/L, 25mg/L, 50mg/L, 100mg/L, 200mg/L, 250mg/L, 300mg/L, 500mg/L, 800mg/L, and 1000 mg/L.
0.01g of the biomagnetic nanocomposite prepared by the above example 2 was weighed, added to 10mL of aqueous solutions of As (III) and As (V) with initial concentrations set in advance, and then the pH of the solutions of As (III) and As (V) was adjusted to 3 with 0.1M HCl or NaOH, respectively, and oscillated in a gas bath constant temperature oscillation tank at a temperature of 25 ℃ and a rotation speed of 180 rpm. Sampling is carried out after oscillation for 24h, an inductively coupled plasma atomic emission spectrometer (ICP OES) is used for measuring As (III) and As (V) in the detection solution, and the adsorption quantity of each material to As (III) and As (V) is calculated.
As shown in FIG. 6, the adsorption amounts of As (III) and As (V) of the biomagnetic nanocomposite material are rapidly increased with the increase of the initial concentration of the arsenic solution, and the maximum adsorption amounts of As (III) and As (V) of the biomagnetic nanocomposite material in the acidic high-concentration arsenic-containing solution reach 572.4mg/g and 548.8mg/g respectively, so that the biomagnetic nanocomposite material has excellent removal performance.
In summary, in the above technical solutions of the present invention, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all equivalent structural changes made by using the contents of the specification and the drawings of the present invention or other related technical fields directly/indirectly applied thereto are included in the scope of the present invention.
Claims (10)
1. A preparation method of a biological magnetic nano composite material is characterized by comprising the following steps:
s1, preparing a nano zero-valent iron-ferroferric oxide double nano material;
s2, embedding the nano zero-valent iron-ferroferric oxide nano material by using polyethyleneimine to obtain the biomagnetic nano composite material.
2. The preparation method according to claim 1, wherein the preparation of the nano zero-valent iron-ferroferric oxide nano material comprises the following steps:
s11, dispersing the ferroferric oxide particles in an aqueous solution to obtain a ferroferric oxide aqueous solution, and then adding a ferrite solution into the ferroferric oxide aqueous solution to obtain a reduction mixed solution;
s12, dropwise adding a borohydride solution into the reduction mixed solution to perform reduction reaction to obtain the nano zero-valent iron-ferroferric oxide nano material;
Wherein, the step S11 and the step S12 are both carried out under the protection of nitrogen.
3. The method for preparing a composite material according to claim 2, wherein the step S12 further includes: and after the reduction reaction is carried out, sequentially separating, washing and drying the product of the reduction reaction to obtain the nano zero-valent iron-ferroferric oxide nano material.
4. The method of claim 2, wherein the ferrous salt solution comprises one of a ferrous sulfate solution, a ferrous chloride solution, and a ferrous nitrate solution; the borohydride solution comprises sodium borohydride or potassium borohydride solution.
5. The method of claim 2, wherein the BH in borohydride solution is4 -With respect to the solubility of Fe in the ferrous salt solution2+Is greater than 2.
6. The preparation method according to any one of claims 1 to 5, wherein in the nano zero-valent iron-ferroferric oxide nano-material, Fe0And Fe3O4The mass ratio of (A) to (B) is 1: 0.3-1: 5.
7. The method for preparing a composite material according to claim 1, wherein the step S2 includes:
s21, dissolving polyethyleneimine in absolute ethyl alcohol to obtain a polyethyleneimine solution; dissolving a nano-grade zero-valent iron-ferroferric oxide nano-grade material in a buffer solution to obtain a zero-valent iron-ferroferric oxide nano-grade solution;
S22, mixing the polyethyleneimine solution and the zero-valent iron-ferroferric oxide nano solution to perform an embedding reaction; and then sequentially separating, washing and drying the product of the embedding reaction to obtain the biomagnetic nano composite material.
8. The method according to claim 7, wherein in the step S21, the volume ratio of the absolute ethyl alcohol to the buffer solution is 1:0.5 to 1: 1;
in the step S22, the concentration of the polyethyleneimine after being dissolved in the absolute ethanol and the buffer solution is 5mg/L to 15 mg/L.
9. A biomagnetic nanocomposite material prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the biomagnetic nanocomposite material according to claim 9 for remediation of acidic arsenic-containing wastewater.
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